Process for the conversion of nonfusible and insoluble polyacroleins



United States Patent r 3,206,433 Ice Patented Sept. 14, 1965 lein itself is of acidic character in the medium employed, 3206433 y it itself will act as the acid catalyst.

:33 It was surprising that it is possible to react the infusible, Werner Kern, Mainz, Otto Schweitzer, Konigstein, insoluble homopolymers of acrolein obtained by spon u u and Rolf Schulz, Maiuz (Rhine), German as. 5 taneous or radical polymerization under the heterogensignors to Deutsche Goldund Silber-Scheideanstalt eous reaction conditions required. That is, the polyacrovormals Roessler, Frankfurt am Main, Germany lein at the beginning of the reaction is present in SOlld un- NO Drawing- Filed June 1962, 201,755 dissolved form and only the resulting derivative goes into Claims P y, apPlieetiee y, 23, 1955, solution as the reaction proceeds. The reaction products 1956 D 22,164 i in contrast to the starting polyacrolein employed are 6 Claims (CL 260 '67) soluble in a number of organic solvents such as benzene, The present invention relates to a process for the treatvy nitfemethane, dimethyl formamide, ment of non-fusible homopolymers of acrolein which conaeeteaeetie e tcr, ethyl t tetfehydfeful'ane, acetone, tain substantially no free aldehyde groups and which are (hexane, PY l and e llkenormally insoluble in normal organic solvents to convert Y pp p Seleetleil 9 the reactants 1t not y them into more valuable products and especially products Pesslble to vary the selubfllty'ef the Products Produced i h are 1 1 1 i a number of Solvents but also other physical properties thereof, such as, for

It is known that unstabilized acrolein spontaneously example, mp e Stability, Within e limitspolymerizes upon standing to produce a solid, non-fusible In y 1I1 StaI1eeS It h been fldvlsable Carry and insoluble product which has been designated as disout the reaetlon aeeordlrlg' 9 the Invention With an acryl (R d b h Li bi A Chem, 47 1 43 cess of the substance which is to react with the acrolein 113). Acrolein furthermore polymerizes under the in- P y especially When the reaction P e is soluble fiuence of radical forming catalysts to product infusible 111511611 excess- Under some elreumstanees, It is also polymers which are insoluble in the known organic sol-f Vantageous to pl y a Solvent ill Which e l wer m l cvents. It therefore was previously assumed that hardly 111211 Weight reactants, as Well as the reaction Product, is any double bonds or aldehyde groups were retained in soluble, even though the polyacrolein itself is insoluble such polymers and that therefore the polyacroleins are untherein. For the production of soluble products, it is suited for the production of polyaldehydes (Houben-Weyl, necessary that the starting materials contain no crossvol. VII, pages 133-135). It was only in certain oligolinkages through principal C--C valence's or contain such 3 mefs 0f acrolein (Gilbert, Y, Amer- Chemcross-linking bonds which are not split under the reaction Soc. 60 (1938), p. 1911), and certain copolymers of conditions acrolein with other vinyl compounds that reactive alde-' The reactions according to the invehtion can usually hyde I- could ascertamefi- The homopolymfirs be carried out at room temperature, but moderately raised of acrokim were prevl'ou.sly copsltiered rather linreactwe temperatures expedite the reaction. Temperatures over and achieved no technical significance (Schildknecht, C often can engenderside reactions which y cause Vinyl and Related Polymers, Wiley and Sons, New York, the reaction product to lose its Solubility. I g

1952 Page 700) The process according to the invention can also be em- Accordmg to the Invention It was unexpectedly dis ployed to obtain polymers which cannot be produced from covered that the homopolymers of acrolein contrary to prior indications do contain aldehyde groups but that these 40 the Correspondmg acrolem monomer either because such are in the form of aldehyde-hydrate-ether groupin and monomer is not available or is lncapable of polymerizing. therefore not free and that the intermolecular ether grollp- In Teactlons of the pelyeeroleln according to e ings are the cause of the cross-linking and therefore their Venue monomeric acrolein is formed and therefore infusibility and insolubility, as indicated in the following the pelyaefoleins do not ve as a source of monomeric formula: acrolein.

Furthermore, according to the invention it was found The products obtained according to the invention can unexpectedly that these masked aldehyde groups which be employed together with other materials to produce are present in all such macromolecular homopolymers of synthetic resins or they can be employed by themselves acrolein which are infusible and normally insoluble in all in the production of coatings or lacquers or for the imcommon organic solvents and which are produced by sponpregnation of textiles. For example, their solutions can taneous or radical polymerization using radical forming 0 be employed for the surface treatment of threads, texcatalysts such as redox systems and are macromolecular, tiles, films, artificial leather, as well as for the treathaving molecular weights above 10,000 (see Staudinger, ment of animal skins and tanned leather produced there- Makromolekulare Chemie & Biologic, page 4, 1947, from. In most instances, solutions containing 'only a few Basel), can be caused to react with the functional alcopercent of the products according to the invention are holic or phenolic hydroxyl or thiol groups as in alcohols, 5 suitable for the surface treatment of textiles.- thioalcohols, phenols and thiophenols in the presence of The following examples will serve to illustrate several an acid catalyst. modifications of the invention:

All acid reacting substances, such as non-oxidizing organic or inorganic acids, such as acetic acid, hydrochloric acid, chl-oroacetic acid, diethyl sulfate, p-toluene sulfonic 7 1 gram of polyacrolein obtain by spontaneous polymacid and the like, can be used as the acid catalyst. In the erization was mixed with 50 cc. of ethyl alcohol and event that the compound to be reacted with the polyacromg. of p-toluene sulfonic acid and the mixture Example 1 ether.

heated under reflux with stirring until complete solution occurred.

Instead of ethyl alcohol, the reaction was also carried out in analogous manner with methanol, n-propanol, n-

days at room temperature. The ratio of p-chlorophenol to acrolein was 811. Complete solution occurred. The reaction product was precipitated with methanol. It was soluble in pyridine 0r dirnethyl formamide.

sulfonic acid and the mixture heated on a water bath to 80 C. with stirring. After 12 hours, cc. of benzene were added and the mixture centrifuged to remove a small quantity of undissolved material. A colorless high molecular weight product was precipitated from the resulting clear yellowish solution by the addition of The product is soluble in benzene, nitrobenzene, dioxane, pyridine, dimethyl formamide and the like. After four-fold reprecipitation, it contained 19% of sulfur. By treatment with peracids, it could be oxidized to the corresponding polymeric sulfones.

Example 3 Example 4 1 g. of an acrolein polymer obtained by bulk polymerization of acrolein with 2.5% benzoyl peroxide at 60 C. (see R. C. Schulz, Makromolekulare Chemie, vol. 17

. .(1955), p. 62) were heated to the boiling temperature with 100 ccm. n-propanol and 100 milligrams p-toluene sulfonic acid. The solution was filtered after 3 hours and poured in cold water. 1.6 g. polymerized acrolein acetal were obtained.

Example 5 560 parts of a polyacrolein of a molecular weight of 56,000 obtained by spontaneous polymerization were 1ntroduced into a solution composed of 9 parts of p-chlorophenol and 1 part of water and p-toluene sulfonic acid as catalyst and t e mixture allowed to stand for 14 butanol, ethylene chlorohydrin, 1,3-butylene glycol, ethyl- 5 Analogous results were obtained using monochloroene .glycol, glycol monoethyl ether, glycolic acid butyl acetic acid or acetic acid instead of the p-toluene sulfonic ester, benzyl alcohol, cyclohexanol or other alcohols. acid as the catalyst. If the temperature employed for Dioxane can, if desired, be employed as a diluent for the reaction was raised to 50 C. solution was completed the reaction. 10 in 12 hours.

The reaction was also analogously carried out with Example 6 i gg s ggg gg ggig ggggg aiigzg g 2: Polyacrolein produced by radical polymerization was erizatign) with analo 3 sults P y placed in a 50% aqueous solution of resorcinol. Comg e plete solution occurred after several days standing at The react1on products can be precipitated from their 15 room temperature Solutlon by appropnate precipltatmg agents example Analogous results were obtained with a 50% aqueous substances WhICh do not dissolve the reaction product, Solution of py r 0021 01 but are miscible with the solvent. For instance, the ethyl alcohol reaction product can be precipitated from p e 7 the resultmg ethyl alcohol sown-On y the addltlon of 20 Further illustrations of reactions carried out according water or Petroleum etherto the invention are tabulated below. The polyacroleins employed in all of the tests, except the one marked with Example 2 an asterisk, were obtained by polymerization of acrolein 1 gram of polyacrolein obtained by spontaneous polymwith benzoyl peroxide. The polyacrolein in that instance erization was added to a mixture containing 10 cc. of 25 w on obtained y spontanous P ymerization.

Polyacrolein, Dioxane, Temper-a Reaction Yield,

mg. Alcohol, cc. cc. Catalyst ture C. time in mg.

minutes 10 methanol p-Toluenesulfonieacid 10% by wt 65 153 (o-Formie acid ethyl ester 0,5 com). 100 10 ethanol p-Toluene sulfonic acid 20% bywt... 80 180 143 100 10 n-Butanol pigpluene sulfome acid 2% by wt 8090 1000 100 11-13 1; 1-.

100 5ethyle r ie c l ilorohydr 5 p-Toluene sullonie acid 2% by wt 60-100 30 165 100 1,3-butyl glycol 5 cc 5 p-Toluene sulfomc acid 20% by wt". 100 60 82 100 l0glycolmonoethylether" p-Toluene sulfonic acid 20%bywt 100 30 100 5glyeolicacid butylester- 5 p-Toluenesullonic acid 20% bywt... 100 480 116 100 5benzyl alcohol 6 p-Toluenesulfonic acid 20% bywt.-. 100 60 187 benzene, 10 cc. of thiophenol and 100 mg. of p-toluene Example 8 The product prepared as indicated in Example 7 (the table line 5) from polyacrolein with n-butan'ol gives useful films if the solution obtained is sprayed or poured on a glass plate and dried. The films are colorless and flexible and not brittle.

This application is a continuation-in-part of application Serial No. 573,349, filed March 23, 1956, now abandoned.

We claim:

1. A process for the conversion of a macromolecular infusible, insoluble homopolymer of acrolein only, containing masked aldehyde groups in the form of aldehydehydrate-ether groups but substantially devoid of free aldehyde groups, selected from the group consisting of polyacroleins obtained by spontaneous polymerization and polyacroleins obtained by radical polymerization to produce polymeric derivatives thereof which are substantially more soluble in selected organic solvents than said homopolymer which comprises reacting such acrolein homopolymer with a substance selected from the group consisting of alcohols, thioalcohols and thiophenols in a non-oxidizing acid medium at a temperature between room temperature and C. to form an acetalized derivative of such homopolymer with said substance.

2. The process of claim 1 in which said acrolein polymer is a polyacrolein obtained by spontaneous polymerization of acrolein.

3. The process of claim 1 in which said acrolein polymer is a. polyacrolein obtained by radical polymerization of acrolein.

4. The process of claim 1 in which said reaction is carried out in an excess of such substance reacted with said polymer.

5. The process of claim 1 in which said reaction is carried out in the presence of a solvent for the substance reacted with said polymer and the reaction product.

6. The derivative of polyacrolein produced by the process of claim 1.

References Cited by the Examiner UNITED STATES PATENTS 6 2,945,837 7/60 Eifert et a1. 260-73 3,055,866 9/62 Oyanagi 260-73 3,079,357 2/63 Fisher 260-67 FOREIGN PATENTS 141,059 12/20 Great Britain.

WILLIAM H. SHORT, Primary Examiner.

JOSEPH R. LIBERMAN, Examiner. 

1. A PROCESS FOR THE CONVERSION OF A MACROMOLECULAR INFUSIBLE, INSOLUBLE HOMOPOLYMER OF ACROLEIN ONLY, CONTAINING MASKED ALDEHYDE GROUPS IN THE FORM OF ALDEHYDEHYDRATE-ETHER GROUPS BY SUBSTANTIALLY DEVOID OF FREE ALDEHYDE GROUPS, SELECTED FROM THE GROUP CONSISTING OF POLYACROLEINS OBTAINED BY SPONTANEOUS POLYMERIZATION AND POLYACROLEINS OBTAINED BY RADICAL POLYMERIZATION TO PRODUCE POLYMERIC DERIVATIVES THEREOF WHICH ARE SUBSTANTIALLY MORE SOLUBLE IN SELECTED ORGANIC SOLVENTS THAN SAID HOMOPOLYMER WHICH COMPRISES REACTING SUCH ACROLEIN HOMOPOLYMER WITH A SUBSTANCE SELECTED FROM THE GROUP CONSISTING OF ALCOHOLS, THIOALCOHOLS AND THIOPHENOLS IN A NON-OXIDIZING ACID MEDIUM AT A TEMPERATURE BETWEEN ROOM TEMPERATURE AND 150*C. TO FORM AN ACETALIZED DERIVATIVE OF SUCH HOMOPOLYMER WITH SAID SUBSTANCE. 